US20220227650A1 - Integrated boron removal and flocculation process for treating fracturing wastewater - Google Patents
Integrated boron removal and flocculation process for treating fracturing wastewater Download PDFInfo
- Publication number
- US20220227650A1 US20220227650A1 US17/616,443 US202017616443A US2022227650A1 US 20220227650 A1 US20220227650 A1 US 20220227650A1 US 202017616443 A US202017616443 A US 202017616443A US 2022227650 A1 US2022227650 A1 US 2022227650A1
- Authority
- US
- United States
- Prior art keywords
- process according
- liquid
- fracturing
- boron
- treated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 56
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002351 wastewater Substances 0.000 title claims abstract description 24
- 238000005189 flocculation Methods 0.000 title claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 45
- 230000008569 process Effects 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 159000000009 barium salts Chemical class 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000011541 reaction mixture Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- 229920002907 Guar gum Polymers 0.000 claims description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000665 guar gum Substances 0.000 claims description 8
- 229960002154 guar gum Drugs 0.000 claims description 8
- 235000010417 guar gum Nutrition 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims description 5
- 235000009496 Juglans regia Nutrition 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 235000020234 walnut Nutrition 0.000 claims description 5
- 239000006004 Quartz sand Substances 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical group [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 4
- 229910001626 barium chloride Inorganic materials 0.000 claims description 4
- 238000010979 pH adjustment Methods 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 240000007049 Juglans regia Species 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 230000016615 flocculation Effects 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000003921 oil Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 14
- 238000011282 treatment Methods 0.000 description 14
- 239000012530 fluid Substances 0.000 description 13
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000001223 reverse osmosis Methods 0.000 description 5
- 241000758789 Juglans Species 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
- C02F1/004—Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/108—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/44—Time
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Definitions
- the present disclosure is related to the field of oil or gas field wastewater treatment, and in particular to an integrated boron removal and flocculation process for treating fracturing flowback liquid.
- Fracturing fluid is essential for hydraulic fracturing. Its preparation requires various additives, including a thickening agent, a cross-linking agent, a sterilizing agent, a high temperature stabilizer and the like, so as to enable the prepared fracturing fluid to have good properties and thus satisfy the requirements of the fracturing operation. At the end of the fracturing operation, 30 to 60% of the fracturing fluid is flowed back to the ground. A fracturing flowback fluid is thus formed.
- the flowback fluid contains the various additives used in the preparation of the fracturing fluid and hazardous substances including formation water and crude oil, and is considered one of the industrial wastewater which is difficult to purify.
- the fracturing flowback fluid is typically and advantageously reused after treatment for the preparation of the fracturing fluid, thereby realizing recycling of water in the fracturing flowback fluid.
- Water quality parameters, including oil content and suspended solids content, of the fracturing flowback fluid having been subjected to oxidation, flocculation, settling and the like can substantially satisfy the requirements for reuse.
- the cross-linking agent containing boron remaining in the fracturing flowback fluid would be previously crosslinked with polymers due to addition of an alkaline additive and thus an increase in pH value. This may cause problems such as blockage of process pipelines and a difficulty in determining the degree of cross-linking, thereby negatively affect the reuse of the flowback fluid.
- CN 1507417 A describes a water processing method, comprising separating boron-containing water in a reverse osmosis membrane module to provide a permeated water; subjecting a portion of the obtained permeated water to boron removal using an adsorbent; and mixing the portion of the permeated water subjected to the boron removal with the other portion not subjected to the boron removal in a certain ratio to provide a mixed water having a low boron content.
- This method is suitable to process water having a boron concentration of equal to or less than 10 mg/L, and can enable the boron concentration to be lowered to 0.05 mg/L or less.
- CN 103298748 A describes a process for treating seawater containing boron by means of using expanded clays with a particle size in the range of 0.2 to 10 mm and a porosity of higher than 40%.
- the process can selectively remove the boron contained therein.
- CN 201610086174 describes a process for substantially removing boron in a lithium chloride solution, comprising three steps of adsorption, elution, and desorption.
- the lithium chloride solution containing boron is fed into an adsorption column packed with boron-removing resin so that the boron ions can be bound to the resin to form a complex.
- a high-purity lithium chloride solution can be obtained.
- the boron concentration can be substantially lowered to 1 mg/L or less by using the process with a boron removal rate of 99.5% or more.
- CN 102703703 B describes a continuous ion exchange device and method for removing boron from salt-lake brine of magnesium chloride, the device comprising a plurality of resin columns packed with a resin, feed manifolds configured to be connected to tops of the resin columns, and discharge manifolds configured to be connected to bottoms of the resin columns. All of the resin columns are sequentially connected in series via pipes to form five sets of resin columns, each set configured to sequentially and cyclically perform adsorption (to remove boron), elution, desorption, back-washing, and replacement (with the final brine) processes by means of control valves arranged on feed branch pipes and discharge branch pipes (i.e., these control valves enable the individual processes to proceed in each set in turn).
- CN 105198054 A describes a process for removing boron from a body of water, comprising: adding magnesium oxide into the body of water containing boron followed by stirring under heating to initially remove the boron; and filtering the resulting solution to obtain a filter, into which an oxidant is added followed by stirring under heating to substantially remove the boron.
- the magnesium oxide as a raw material in the process is cheap and easily available.
- the boron removal process described in CN 105198054 A causes no loss of the magnesium content in the body of water.
- the body of water to be treated can be a body of water having a high boron content, such as subsurface brine, salt-lake brine, industrial wastewater, and seawater, and the boron content can be reduced to 5 mg/L or less by using the process.
- the process is simple and low cost.
- CN 109485185 A describes a pulse electrochemical process and device for treating oil field wastewater.
- the process comprises aerating the oil field wastewater to be treated; performing electrochemical treatment for the aerated oil field wastewater with a pulse power source at a predetermined current density; subjecting the oil field wastewater after the electrochemical treatment to pH adjustment, followed by addition of auxiliary agents to carry out coagulation and precipitation treatments, thereby completing the electro-flocculation treatment for the oil field wastewater.
- the device comprises a pH-regulating tank, an electrochemical reaction system, and a coagulation tank.
- CN 103043831 relates to the field of wastewater treatment, in particular treatment of wastewater generated from continental shale gas production, and especially to a process for treating wastewater from continental shale gas well fracturing.
- the process is characterized by five steps, performed sequentially, of pH adjustment, oxidation (thus reduction in viscosity), flocculation and settling, solid-liquid separation and then adsorption and filtration.
- the wastewater after treatment using the process can be recycled to the fracturing liquid preparation or to be injected back into stratum, which saves water and is beneficial to the environment.
- the process may be performed as follows: adjusting the pH of the wastewater to pH 5.5; adding 0.15% hydrogen peroxide thereto, followed by stirring for 15 minutes to carry out a reaction; adjusting the pH of the resulting solution to pH 8.0, followed by addition of 50 mg/L polyaluminum chloride and 2 mg/L anionic polyacrylamide; and allowing the solution to stand still for 10 minutes before filtration.
- CN 104743713 B describes a device for treating wastewater from oil field well drilling and measure well operation, which can prevent any components of the wastewater from falling onto the ground and comprises a pressure reduction and sand removal unit, a coagulation and settling unit for removing mud, a water purification unit, a sludge solidification unit, a gas feeding unit, and a drug feeding unit.
- the high-pressure fracturing flowback liquid from oil field well drilling and measure well operation is fed into the pressure reduction and sand removal unit to subject to pressure reduction and oil-sand-liquid separation.
- the separated liquid is fed into the coagulation and settling tank via a multi-purpose pump for water-mud separation.
- the separated effluent is pumped into a three-stage treatment tank of the water purification unit via a pressure pump for purification treatment. Oil, sand, and water produced by the purification treatment are each recycled.
- the concentrated sludge is subjected to solidification treatment by the sludge solidification unit to form clods, which are then transported to biosafety disposal sites. During this whole treatment process, none of the oil, mud, and water falls to the ground.
- the device is reasonably designed, and allows the treatment process using it to provide high resource utilization and be environmentally friendly.
- CN 106630309 A describes a system for treating downhole operation wastewater.
- the system comprises a reactor, where the wastewater is subjected to oxidation so that high-molecular organic compounds therein are degraded and the content of dichromates is thus reduced; and a reverse osmosis unit, where the wastewater having been subjected to the oxidation process is subjected to reverse osmosis to produce a concentrated solution and permeate which can be discharged directly.
- impurities present in the wastewater can be removed therefrom through the oxidation and reverse osmosis processes, so that the wastewater can be discharged as treated water capable of meeting the emission standard and pollution of the soil by the wastewater can thus be prevented.
- An objective of the present disclosure is to provide an integrated boron removal and flocculation process for treating fracturing wastewater.
- an integrated boron removal and flocculation process for treating fracturing wastewater or fracturing flowback liquid comprising steps of: adjusting a pH level of the fracturing flowback liquid to be treated with an alkali to a range of 8.5 to 10.0; adding an oxidant to the flowback liquid after pH adjustment to carry out a reaction at room temperature for 30 to 120 minutes; adding a barium salt to the reaction mixture resulting from the reaction to carry out a further reaction at room temperature for 30 to 120 minutes; and allowing the reaction mixture resulting from the preceding step to stand still and settle before filtration via a filtration unit.
- the alkali may be a 10 to 30 wt. % aqueous sodium hydroxide or potassium hydroxide solution.
- the barium salt may be barium chloride or barium nitrate.
- the ratio of the barium salt used to the fracturing flowback liquid may be 100-150 mg:1 L.
- the oxidant may be a 25 to 30 wt. % aqueous hydrogen peroxide solution or a 12 to 15 wt. % aqueous sodium hypochlorite solution.
- the volume of the oxidant used may be 0.15 to 0.5 vol. % of that of the fracturing flowback liquid to be treated.
- the fracturing flowback liquid to be treated may have a boron content of 100 to 200 mg/L.
- the fracturing flowback liquid to be treated may be a guar gum base liquid or a guar gum-polymer base liquid, wherein the polymer in the guar gum-polymer base liquid may be partially crosslinked polyacrylamide with a viscosity-average molecular weight of 12,000,000 to 18,000,000; and the ratio of the guar gum to the polymer may be 3:1 to 5:1 by weight.
- the stand still and settling step may last for 20 to 40 minutes.
- the filtration unit may be formed by two filters, in series, selected from the group consisting of walnut shell, quartz sand, and modified fibrous ball filters.
- the state of the boron in the fracturing flowback liquid can be changed by adjusting the pH thereof to become alkaline and then adding thereto an oxidant to carry out a reaction for a certain time period, and the boron in the changed state can then be reacted with the barium salt added thereafter to produce a precipitate.
- the stability of the flowback liquid can be deteriorated by the addition of the oxidant.
- Suspended solids in the flowback liquid can be removed through adsorption, wrapping, and then settling by the action of the precipitate formed (a barium salt).
- the process of the present disclosure has several advantages.
- the boron content in the liquid was reduced from 154 mg/L to 28 mg/L with a boron removal rate of 80%, and the suspended solids and oil contents were reduced from 85 mg/L and 60 mg/L to 5.0 mg/L and 3.0 mg/L, respectively.
- the resulting reaction mixture was allowed to stand still and settle for 20 minutes, and then was filtered via one quartz sand filter and one modified fibrous ball filter arranged in series. It was found that the boron content in the liquid was reduced from 143 mg/L to 14.1 mg/L with a boron removal rate of 90%, and the suspended solids and oil contents were reduced from 106 mg/L and 80 mg/L to 4.0 mg/L and 2.0 mg/L, respectively.
- the boron content in the liquid was reduced from 103 mg/L to 9.7 mg/L with a boron removal rate of 90%, and the suspended solids and oil contents were reduced from 110 mg/L and 108 mg/L to 6.0 mg/L and 4.0 mg/L, respectively.
- the resulting reaction mixture was allowed to stand still and settle for 40 minutes, and then was filtered via one walnut shell filter and one modified fibrous ball filter arranged in series. It was found that the boron content in the liquid was reduced from 123 mg/L to 11.7 mg/L with a boron removal rate of 90% or greater, and the suspended solids and oil contents were reduced from 97 mg/L, and 68 mg/L, to 5.0 mg/L, and 2.0 mg/L, respectively.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
Description
- This application claims the benefit of priority of Chinese Application No. 201910747901.X filed Aug. 14, 2019, entitled “INTEGRATED BORON REMOVAL AND FLOCCULATION PROCESS FOR TREATING FRACTURING WASTEWATER”, the entire disclosure of which is incorporated herein by reference.
- The present disclosure is related to the field of oil or gas field wastewater treatment, and in particular to an integrated boron removal and flocculation process for treating fracturing flowback liquid.
- Fracturing fluid is essential for hydraulic fracturing. Its preparation requires various additives, including a thickening agent, a cross-linking agent, a sterilizing agent, a high temperature stabilizer and the like, so as to enable the prepared fracturing fluid to have good properties and thus satisfy the requirements of the fracturing operation. At the end of the fracturing operation, 30 to 60% of the fracturing fluid is flowed back to the ground. A fracturing flowback fluid is thus formed. The flowback fluid contains the various additives used in the preparation of the fracturing fluid and hazardous substances including formation water and crude oil, and is considered one of the industrial wastewater which is difficult to purify. Currently, the fracturing flowback fluid is typically and advantageously reused after treatment for the preparation of the fracturing fluid, thereby realizing recycling of water in the fracturing flowback fluid.
- Water quality parameters, including oil content and suspended solids content, of the fracturing flowback fluid having been subjected to oxidation, flocculation, settling and the like can substantially satisfy the requirements for reuse. However, during the subsequent preparation of the fracturing fluid, the cross-linking agent containing boron remaining in the fracturing flowback fluid would be previously crosslinked with polymers due to addition of an alkaline additive and thus an increase in pH value. This may cause problems such as blockage of process pipelines and a difficulty in determining the degree of cross-linking, thereby negatively affect the reuse of the flowback fluid.
- CN 1507417 A describes a water processing method, comprising separating boron-containing water in a reverse osmosis membrane module to provide a permeated water; subjecting a portion of the obtained permeated water to boron removal using an adsorbent; and mixing the portion of the permeated water subjected to the boron removal with the other portion not subjected to the boron removal in a certain ratio to provide a mixed water having a low boron content. This method is suitable to process water having a boron concentration of equal to or less than 10 mg/L, and can enable the boron concentration to be lowered to 0.05 mg/L or less.
- CN 103298748 A describes a process for treating seawater containing boron by means of using expanded clays with a particle size in the range of 0.2 to 10 mm and a porosity of higher than 40%. In the event that the seawater to be treated is at a pH of 8.2 and has a boron concentration of 4 to 5 mg/L, the process can selectively remove the boron contained therein.
- CN 201610086174 describes a process for substantially removing boron in a lithium chloride solution, comprising three steps of adsorption, elution, and desorption. In particular, the lithium chloride solution containing boron is fed into an adsorption column packed with boron-removing resin so that the boron ions can be bound to the resin to form a complex. Thus, a high-purity lithium chloride solution can be obtained. For the lithium chloride solution having a boron concentration of 5 to 8000 mg/L, the boron concentration can be substantially lowered to 1 mg/L or less by using the process with a boron removal rate of 99.5% or more.
- CN 102703703 B describes a continuous ion exchange device and method for removing boron from salt-lake brine of magnesium chloride, the device comprising a plurality of resin columns packed with a resin, feed manifolds configured to be connected to tops of the resin columns, and discharge manifolds configured to be connected to bottoms of the resin columns. All of the resin columns are sequentially connected in series via pipes to form five sets of resin columns, each set configured to sequentially and cyclically perform adsorption (to remove boron), elution, desorption, back-washing, and replacement (with the final brine) processes by means of control valves arranged on feed branch pipes and discharge branch pipes (i.e., these control valves enable the individual processes to proceed in each set in turn).
- CN 105198054 A describes a process for removing boron from a body of water, comprising: adding magnesium oxide into the body of water containing boron followed by stirring under heating to initially remove the boron; and filtering the resulting solution to obtain a filter, into which an oxidant is added followed by stirring under heating to substantially remove the boron. The magnesium oxide as a raw material in the process is cheap and easily available. The boron removal process described in CN 105198054 A causes no loss of the magnesium content in the body of water. The body of water to be treated can be a body of water having a high boron content, such as subsurface brine, salt-lake brine, industrial wastewater, and seawater, and the boron content can be reduced to 5 mg/L or less by using the process. The process is simple and low cost.
- CN 109485185 A describes a pulse electrochemical process and device for treating oil field wastewater. The process comprises aerating the oil field wastewater to be treated; performing electrochemical treatment for the aerated oil field wastewater with a pulse power source at a predetermined current density; subjecting the oil field wastewater after the electrochemical treatment to pH adjustment, followed by addition of auxiliary agents to carry out coagulation and precipitation treatments, thereby completing the electro-flocculation treatment for the oil field wastewater. The device comprises a pH-regulating tank, an electrochemical reaction system, and a coagulation tank.
- CN 103043831 relates to the field of wastewater treatment, in particular treatment of wastewater generated from continental shale gas production, and especially to a process for treating wastewater from continental shale gas well fracturing. The process is characterized by five steps, performed sequentially, of pH adjustment, oxidation (thus reduction in viscosity), flocculation and settling, solid-liquid separation and then adsorption and filtration. The wastewater after treatment using the process can be recycled to the fracturing liquid preparation or to be injected back into stratum, which saves water and is beneficial to the environment. In particular, the process may be performed as follows: adjusting the pH of the wastewater to pH 5.5; adding 0.15% hydrogen peroxide thereto, followed by stirring for 15 minutes to carry out a reaction; adjusting the pH of the resulting solution to pH 8.0, followed by addition of 50 mg/L polyaluminum chloride and 2 mg/L anionic polyacrylamide; and allowing the solution to stand still for 10 minutes before filtration.
- CN 104743713 B describes a device for treating wastewater from oil field well drilling and measure well operation, which can prevent any components of the wastewater from falling onto the ground and comprises a pressure reduction and sand removal unit, a coagulation and settling unit for removing mud, a water purification unit, a sludge solidification unit, a gas feeding unit, and a drug feeding unit. When in use, the high-pressure fracturing flowback liquid from oil field well drilling and measure well operation is fed into the pressure reduction and sand removal unit to subject to pressure reduction and oil-sand-liquid separation. The separated liquid is fed into the coagulation and settling tank via a multi-purpose pump for water-mud separation. The separated effluent is pumped into a three-stage treatment tank of the water purification unit via a pressure pump for purification treatment. Oil, sand, and water produced by the purification treatment are each recycled. The concentrated sludge is subjected to solidification treatment by the sludge solidification unit to form clods, which are then transported to biosafety disposal sites. During this whole treatment process, none of the oil, mud, and water falls to the ground. The device is reasonably designed, and allows the treatment process using it to provide high resource utilization and be environmentally friendly.
- CN 106630309 A describes a system for treating downhole operation wastewater. The system comprises a reactor, where the wastewater is subjected to oxidation so that high-molecular organic compounds therein are degraded and the content of dichromates is thus reduced; and a reverse osmosis unit, where the wastewater having been subjected to the oxidation process is subjected to reverse osmosis to produce a concentrated solution and permeate which can be discharged directly. With the system, impurities present in the wastewater can be removed therefrom through the oxidation and reverse osmosis processes, so that the wastewater can be discharged as treated water capable of meeting the emission standard and pollution of the soil by the wastewater can thus be prevented.
- From the above, it is seen that no removal of boron is described in the oil fracturing wastewater treatment and the oil field wastewater treatment. Few treatment processes for the oil fracturing wastewater are disclosed involving removal of boron, and in these processes, the removal of boron is carried out separately from flocculation, which may cause problems such as long process flow and high cost. In these processes, the removal of boron proceeds mostly by combining adsorption and reverse osmosis.
- An objective of the present disclosure is to provide an integrated boron removal and flocculation process for treating fracturing wastewater.
- Accordingly, the objective of the present disclosure is realized by an integrated boron removal and flocculation process for treating fracturing wastewater or fracturing flowback liquid, comprising steps of: adjusting a pH level of the fracturing flowback liquid to be treated with an alkali to a range of 8.5 to 10.0; adding an oxidant to the flowback liquid after pH adjustment to carry out a reaction at room temperature for 30 to 120 minutes; adding a barium salt to the reaction mixture resulting from the reaction to carry out a further reaction at room temperature for 30 to 120 minutes; and allowing the reaction mixture resulting from the preceding step to stand still and settle before filtration via a filtration unit.
- The alkali may be a 10 to 30 wt. % aqueous sodium hydroxide or potassium hydroxide solution.
- The barium salt may be barium chloride or barium nitrate. The ratio of the barium salt used to the fracturing flowback liquid may be 100-150 mg:1 L.
- The oxidant may be a 25 to 30 wt. % aqueous hydrogen peroxide solution or a 12 to 15 wt. % aqueous sodium hypochlorite solution. The volume of the oxidant used may be 0.15 to 0.5 vol. % of that of the fracturing flowback liquid to be treated.
- The fracturing flowback liquid to be treated may have a boron content of 100 to 200 mg/L. The fracturing flowback liquid to be treated may be a guar gum base liquid or a guar gum-polymer base liquid, wherein the polymer in the guar gum-polymer base liquid may be partially crosslinked polyacrylamide with a viscosity-average molecular weight of 12,000,000 to 18,000,000; and the ratio of the guar gum to the polymer may be 3:1 to 5:1 by weight.
- The stand still and settling step may last for 20 to 40 minutes.
- The filtration unit may be formed by two filters, in series, selected from the group consisting of walnut shell, quartz sand, and modified fibrous ball filters.
- In accordance with the above-described embodiments of the present disclosure, the state of the boron in the fracturing flowback liquid can be changed by adjusting the pH thereof to become alkaline and then adding thereto an oxidant to carry out a reaction for a certain time period, and the boron in the changed state can then be reacted with the barium salt added thereafter to produce a precipitate. The stability of the flowback liquid can be deteriorated by the addition of the oxidant. Suspended solids in the flowback liquid can be removed through adsorption, wrapping, and then settling by the action of the precipitate formed (a barium salt). Compared with the prior art, the process of the present disclosure has several advantages.
-
- With the embodiments of the present disclosure, the removal of boron and flocculation occur simultaneously instead of separately, realizing integration thereof and overcoming problems in the existing processes for preparing the fracturing liquid from the fracturing flowback liquid, for example, they requires a long process line and a large number of devices;
- Impurities such as suspended solids and oil present in the fracturing flowback liquid can be removed through adsorption, wrapping, and then settling by the action of the precipitate produced from the boron removal, so no additional inorganic flocculant is needed and the amount of sludge produced is reduced. The boron removal rate can reach 80% or greater. The contents of the suspended solids and oil present in the fracturing flowback liquid after filtration each can be lowered to less than 5.0 mg/L.
- The embodiments of the present disclosure will be further described in detail with reference to examples, but the disclosure is not limited to these examples.
- 1000 mL of guar gum base fracturing flowback liquid (water base liquid) was taken and the pH was adjusted to 10 using 30 wt. % aqueous sodium hydroxide solution. 2 mL of 30 wt. % aqueous hydrogen peroxide solution was then added to the liquid to carry out a reaction at room temperature for 120 minutes. Thereafter, 150 mg of barium chloride was added to carry out a further reaction at room temperature for 30 minutes. The resulting reaction mixture was allowed to stand still and settle for 30 minutes, and then was filtered via one walnut shell filter and one quartz sand filter arranged in series. It was found that the boron content in the liquid was reduced from 154 mg/L to 28 mg/L with a boron removal rate of 80%, and the suspended solids and oil contents were reduced from 85 mg/L and 60 mg/L to 5.0 mg/L and 3.0 mg/L, respectively.
- 1000 mL of guar gum-polymer (polyacrylamide with a viscosity-average molecular weight of 12,000,000; mass ratio of the guar gum to the polymer=3:1) base fracturing flowback liquid (water base liquid) was taken and the pH was adjusted to 9.5 using 20 wt. % aqueous sodium hydroxide solution. 5 mL of 12 wt. % aqueous sodium hypochlorite solution was then added to the liquid to carry out a reaction at room temperature for 90 minutes. Thereafter, 120 mg of barium nitrate was added to carry out a further reaction at room temperature for 40 minutes. The resulting reaction mixture was allowed to stand still and settle for 20 minutes, and then was filtered via one quartz sand filter and one modified fibrous ball filter arranged in series. It was found that the boron content in the liquid was reduced from 143 mg/L to 14.1 mg/L with a boron removal rate of 90%, and the suspended solids and oil contents were reduced from 106 mg/L and 80 mg/L to 4.0 mg/L and 2.0 mg/L, respectively.
- 1000 mL of guar gum base fracturing flowback liquid (water base liquid) was taken and the pH was adjusted to 8.5 using 10 wt. % aqueous sodium hydroxide solution. 4 mL of 25 wt. % aqueous hydrogen peroxide solution was then added to the liquid to carry out a reaction at room temperature for 90 minutes. Thereafter, 100 mg of barium chloride was added to carry out a further reaction at room temperature for 100 minutes. The resulting reaction mixture was allowed to stand still and settle for 30 minutes, and then was filtered via one walnut shell filter and one modified fibrous ball filter arranged in series. It was found that the boron content in the liquid was reduced from 103 mg/L to 9.7 mg/L with a boron removal rate of 90%, and the suspended solids and oil contents were reduced from 110 mg/L and 108 mg/L to 6.0 mg/L and 4.0 mg/L, respectively.
- 1000 mL of guar gum-polymer (polyacrylamide with a viscosity-average molecular weight of 18,000,000; mass ratio of the guar gum to the polymer=5:1) base fracturing flowback liquid (water base liquid) was taken and the pH was adjusted to 10 using 30 wt. % aqueous potassium hydroxide solution. 3 mL of 15 wt. % aqueous sodium hypochlorite solution was then added to the liquid to carry out a reaction at room temperature for 30 minutes. Thereafter, 130 mg of barium nitrate was added to carry out a further reaction at room temperature for 90 minutes. The resulting reaction mixture was allowed to stand still and settle for 40 minutes, and then was filtered via one walnut shell filter and one modified fibrous ball filter arranged in series. It was found that the boron content in the liquid was reduced from 123 mg/L to 11.7 mg/L with a boron removal rate of 90% or greater, and the suspended solids and oil contents were reduced from 97 mg/L, and 68 mg/L, to 5.0 mg/L, and 2.0 mg/L, respectively.
- The above are only preferred embodiments of the present disclosure. It will be understood that various modifications and improvements may be made without departing from the scope and principle of the disclosure.
Claims (12)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910747901.XA CN110526442B (en) | 2019-08-14 | 2019-08-14 | Method for treating fracturing waste liquid by integrating boron removal and flocculation |
CN201910747901.X | 2019-08-14 | ||
PCT/CN2020/107113 WO2021027654A1 (en) | 2019-08-14 | 2020-08-05 | Method for carrying out boron-removal and flocculation integrated treatment on fracturing waste liquid |
Publications (1)
Publication Number | Publication Date |
---|---|
US20220227650A1 true US20220227650A1 (en) | 2022-07-21 |
Family
ID=68663051
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/616,443 Pending US20220227650A1 (en) | 2019-08-14 | 2020-08-05 | Integrated boron removal and flocculation process for treating fracturing wastewater |
Country Status (3)
Country | Link |
---|---|
US (1) | US20220227650A1 (en) |
CN (1) | CN110526442B (en) |
WO (1) | WO2021027654A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110526442B (en) * | 2019-08-14 | 2021-08-24 | 西安石油大学 | Method for treating fracturing waste liquid by integrating boron removal and flocculation |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7824552B2 (en) * | 2007-09-05 | 2010-11-02 | Halliburton Energy Services, Inc. | Mobile systems and methods of sufficiently treating water so that the treated water may be utilized in well-treatment operations |
US10105653B2 (en) * | 2012-08-13 | 2018-10-23 | Enviro Water Minerals Company, Inc. | System for rinsing electrodialysis electrodes |
US10189733B2 (en) * | 2012-08-13 | 2019-01-29 | Enviro Water Minerals Company, Inc. | Heating system for desalination |
CN106673268A (en) * | 2017-02-27 | 2017-05-17 | 华油惠博普科技股份有限公司 | Oil-gas field sewage treatment system and treatment process thereof |
CN110526442B (en) * | 2019-08-14 | 2021-08-24 | 西安石油大学 | Method for treating fracturing waste liquid by integrating boron removal and flocculation |
-
2019
- 2019-08-14 CN CN201910747901.XA patent/CN110526442B/en active Active
-
2020
- 2020-08-05 US US17/616,443 patent/US20220227650A1/en active Pending
- 2020-08-05 WO PCT/CN2020/107113 patent/WO2021027654A1/en active Application Filing
Also Published As
Publication number | Publication date |
---|---|
CN110526442B (en) | 2021-08-24 |
WO2021027654A1 (en) | 2021-02-18 |
CN110526442A (en) | 2019-12-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8790514B2 (en) | Waste water treatment method | |
US7722770B2 (en) | Method for treating produced water | |
CN105384316B (en) | A kind of processing method of the fluorine-containing nitrogen-containing wastewater of electronics industry | |
CN102126806B (en) | Method for completely recycling wastewater containing fluorine and ammonia nitrogen in electronic industry | |
KR20080063287A (en) | Water treatment method comprising a rapid settling step followed by a filltration step that is performed directly on the micro- or ultra-filtration membranes and corresponding device | |
CA2869833A1 (en) | Method and apparatus for treating accompanied water from well | |
CN103288310B (en) | Slack coal pressure gasification wastewater treatment method and treatment system as well as application | |
CN106315903A (en) | Method for processing shale gas fracturing flowback fluid | |
CN109626715A (en) | The method for reducing ammonia load in processing percolate biochemical system | |
CN207130086U (en) | A kind of salt-containing waste water treating device | |
CN108975638A (en) | A kind of method of the processing of oilfield drilling waste liquid | |
JP2017114705A (en) | Method for producing sodium hypochlorite, and sodium hypochlorite production device | |
CN106630350A (en) | Zero-drainage technology of biochemical effluent water deep treatment and resource recycling of coal chemical industry wastewater | |
CN113200646A (en) | Resource treatment method and system for fracturing flowback fluid | |
CA2657072C (en) | Waste water treatment method | |
CN105417898A (en) | Method for treating reverse osmosis concentrated water and ultrafiltration back washing water in double-membrane method system | |
US20220227650A1 (en) | Integrated boron removal and flocculation process for treating fracturing wastewater | |
KR102052572B1 (en) | Method of treating underground water using chlorine disinfection | |
CN207671875U (en) | A kind of processing system of dyeing waste water | |
CN215161851U (en) | Fracturing flow-back fluid recycling treatment system | |
CN105461107A (en) | Water resource recovering technology for coking wastewater biochemical treatment effluent | |
WO2022246823A1 (en) | Concentrated brine deep purification device and process | |
CN113277653A (en) | Desulfurization wastewater treatment system and method | |
US20160101999A1 (en) | Method of treating suspended solids and heavy metal ions in sewage | |
CN110054358A (en) | A kind of mine water treatment technique |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: CHINA NATIONAL PETROLEUM CORPORATION SAFETY AND ENVIRONMENTAL TECHNOLOGY RESEARCH INSTITUTE CO., LTD., CHINA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YU, TAO;QU, CHENGTUN;LI, JINLING;AND OTHERS;REEL/FRAME:058284/0154 Effective date: 20210624 Owner name: XI'AN SHIYOU UNIVERSITY, CHINA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YU, TAO;QU, CHENGTUN;LI, JINLING;AND OTHERS;REEL/FRAME:058284/0154 Effective date: 20210624 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |